Curable compositions

ABSTRACT

Embodiments include curable compositions including a resin component and a hardener component. The resin component can include an epoxy compound that is selected from the group consisting of aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and combinations thereof, and a reactive diluent that includes a polymeric glycidyl ether. The hardener component can include an adduct and a Mannich base.

FIELD OF DISCLOSURE

This disclosure relates to curable compositions, and in particularcurable compositions that include a resin component and a hardenercomponent.

BACKGROUND

Epoxy systems consist of two components that can chemically react witheach other to form a cured epoxy, which is a hard, duroplastic material.The first component is an epoxy resin and the second component is acuring agent, sometimes called a hardener. Epoxy resins are substancesor mixtures which contain epoxide groups. The hardener can includecompounds which are reactive to the epoxide groups of the epoxy resins.

The epoxy resins can be crosslinked, also referred to as curing, by thechemical reaction of the epoxide groups and the compounds of thehardener. This curing converts the epoxy resins, which have a relativelylow molecular weight, into relatively high molecular weight materials bychemical addition of the compounds of the hardener. Additionally, thehardener can contribute to many of the properties of the cured epoxy.

Some of the hardeners, however, suffer from the disadvantage that theycontain up to 50 weight percent free (alkyl)phenol and/or volatileorganic compounds like benzyl alcohol. Volatile organic compounds aredefined in various terms depending upon region. For example, in theEuropean Union one definition of a volatile organic compound is anyorganic compound having an initial boiling point less than or equal to250 degrees Celsius measured at a standard atmospheric pressure of 101.3kilopascal.

In recent years due to environmental concerns and governmentalregulations, there have been increased efforts made to develop curableepoxy systems which contain a minimum of volatile organic compoundsand/or comply with governmental regulations.

As noted above, epoxy resins can be crosslinked in order to developcertain characteristics. Blushing can occur during the crosslinking.Blushing, sometimes also referred to as whitening, can occur whenmoisture, such as atmospheric water or water that originates from withina porous substrate together with atmospheric carbon dioxide, reacts witha curable composition having a hardener that includes an amine compound.Amine compounds on the surface of the curable composition can combinewith the water and the carbon dioxide to form carbamates. The aminecompounds, which were intended to react with the epoxide groups of theepoxy resins, are consumed and thus not all epoxy resins can crosslinkduring curing. Blushing can produce white patches or hazy effectportions in clear coatings. This can contribute to discoloration overtime, and may cause lack of gloss in pigmented coatings. Furthermore,blushing can affect the coating performance and result in poorovercoatability. Poor overcoatability is the insufficient adhesion of asubsequent coating layer due to a surface energy modification associatedwith the blushing.

SUMMARY

The present disclosure provides one or more embodiments of curablecompositions. For one or more of the embodiments, the curablecompositions include a resin component and a hardener component. Theresin component includes an epoxy compound and a reactive diluent. Theepoxy compound is selected from the group consisting of aromatic epoxycompounds, alicyclic epoxy compounds, aliphatic epoxy compounds, andcombinations thereof. The reactive diluent includes a polymeric glycidylether. The hardener component includes an adduct and a Mannich base.

For one or more of the embodiments, the present disclosure provides anarticle that includes a substrate and a coating on the substrate,wherein the coating includes a cured composition that is obtained fromthe curable compositions, as described herein.

DETAILED DESCRIPTION

“Polymer” and “polymeric” as used herein refer to compounds having astructure that results mainly from the repetition of low molar massunits (monomers), such that over 50 percent of the weight for thatcompound consists of polymer molecules. A “polymer molecule” is amolecule that contains a sequence of at least 3 monomer units, which arecovalently bound to at least one other monomer unit or other reactant;the amount of molecules presenting the same molecular weight must beless than 50 weight percent of the substance.

“Volatile organic compound” as used herein refers to an organic compoundhaving an initial boiling point less than or equal to 250 degreesCelsius measured at a standard atmospheric pressure of 101.3 kilopascal.

“Pot life” as used herein refers to a period of time, at a giventemperature, that a mixture of a resin component and a hardenercomponent remains workable for a particular application. One method ofdetermining pot life includes placing a 100 gram mixture of a resincomponent and a hardener component into a container. A coiled steel wiremoves up and down through the mixture at a moderate speed. As theviscosity of the mixture increases during the curing, the mixture turnsviscous in the course of the curing reaction the wire is no longer ableto move through the mixture and the mixture and the container are liftedto activate a switch. The pot life can be defined as the time periodbeginning when the resin component and the hardener component are mixedand ending when the switch is activated.

The curable compositions of the present disclosure include a resincomponent and a hardener component. For one or more of the embodiments,the resin component includes an epoxy compound, which refers to acompound in which an oxygen atom is directly attached to two adjacent ornon-adjacent carbon atoms of a carbon chain or ring system.

The epoxy compound is selected from the group consisting of aromaticepoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds,and combinations thereof. Examples of aromatic epoxy compounds include,but are not limited to, glycidyl ether compounds of polyphenols, such ashydroquinone, resorcinol, bisphenol A, bisphenol F,4,4′-dihydroxybiphenyl, novolac, tetrabromobisphenol A,2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and1,6-dihydroxynaphthalene.

Examples of alicyclic epoxy compounds include, but are not limited to,polyglycidyl ethers of polyols having at least one alicyclic ring, orcompounds including cyclohexene oxide or cyclopentene oxide obtained byepoxidizing compounds including a cyclohexene ring or cyclopentene ringwith an oxidizer. Some particular examples include, but are not limitedto hydrogenated bisphenol A diglycidyl ether;3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate;3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate;6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate;3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate;3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate; bis(3,4-epoxycyclohexylmethyl)adipate;methylene-bis(3,4-epoxycyclohexane);2,2-bis(3,4-epoxycyclohexyl)propane; dicyclopentadiene diepoxide;ethylene-bis(3,4-epoxycyclohexane carboxylate); dioctylepoxyhexahydrophthalate; and di-2-ethylhexyl epoxyhexahydrophthalate.

Examples of aliphatic epoxy compounds include, but are not limited to,polyglycidyl ethers of aliphatic polyols or alkylene-oxide adductsthereof, polyglycidyl esters of aliphatic long-chain polybasic acids,homopolymers synthesized by vinyl-polymerizing glycidyl acrylate orglycidyl methacrylate, and copolymers synthesized by vinyl-polymerizingglycidyl acrylate or glycidyl methacrylate and other vinyl monomers.Some particular examples include, but are not limited to glycidyl ethersof polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanedioldiglycidyl ether; a triglycidyl ether of glycerin; a triglycidyl etherof trimethylol propane; a tetraglycidyl ether of sorbitol; ahexaglycidyl ether of dipentaerythritol; a diglycidyl ether ofpolyethylene glycol; and a diglycidyl ether of polypropylene glycol;polyglycidyl ethers of polyether polyols obtained by adding one type, ortwo or more types, of alkylene oxide to aliphatic polyols such aspropylene glycol, trimethylol propane, and glycerin; and diglycidylesters of aliphatic long-chain dibasic acids.

For one or more of the embodiments, the resin component further includesa reactive diluent. Reactive diluents are compounds that participate ina chemical reaction with the hardener component during the curingprocess and become incorporated into the cured composition. Reactivediluents can also be used to vary the viscosity and/or cure propertiesof the curable compositions for various applications. For someapplications reactive diluents can impart a lower viscosity to influenceflow properties, extend pot life and/or improve adhesion properties ofthe curable compositions. For one or more of the embodiments, thereactive diluent is less than 60 weight percent of a total weight of theresin component.

For one or more of the embodiments, the reactive diluent is a polymericglycidyl ether. The polymeric glycidyl ether is formed from units whichinclude polyalkylen oxide reacted with epichlorohydrin to form glycidylethers. The glycidyl ether can be selected from the group consisting ofallyl glycidyl ethers, diglycidyl ethers, phenyl glycidyl ethers, alkylglycidyl ether, and combinations thereof. Sometimes, polymeric glycidylethers can be formed by a reaction of mono- to poly-hydroxyl compoundswith alkylen oxides and a conversion of the polyetherpolyol reactionproduct into a glycidyl ether with epichlorohydrin and subsequenttreatment of the former intermediate with an aqueous sodium hydroxide(NaOH) solution. The polymeric glycidyl ether has an average molecularweight of from 650 to 1450. An example of the polymeric glycidyl etherincludes, but is not limited to, a triglycidyl ether oftrimethylolpropan octadeca ethoxilate.

For one or more of the embodiments, the hardener component includes anadduct. Adducts are less hygroscopic and have a lower vapor pressurecompared to some non-adducted amines, as discussed above, and can helpprevent blushing.

The adducts are formed by combination of two or more separate compounds.Compound refers to a substance composed of atoms or ions of two or moreelements in chemical combination. Herein, the two separate compoundsthat are combined are the epoxy compound and a first amine. An amine isa compound that contains an N—H moiety. The adducts are a reactionproduct of the addition reaction of the epoxy compound and the firstamine. The two separate compounds are combined such that there is changein connectivity but no loss of atoms within the compounds. For one ormore of the embodiments an equivalent ratio of one to one, epoxycompound to first amine, is employed when forming the adduct. However,embodiments are not limited to this equivalent ratio of epoxy compoundto first amine when forming the adduct and other equivalent ratios arepossible. For one or more of the embodiments, the adduct is from 10weight percent to 90 weight percent of a total weight of the hardenercomponent.

For one or more of the'embodiments, the first amine is selected from thegroup consisting of aliphatic polyamines, arylaliphatic polyamines,cycloaliphatic polyamines, aromatic polyamines, heterocyclic polyamines,polyalkoxypolyamines, and combinations thereof. The alkoxy group of thepolyalkoxypolyamines is an oxyethylene, oxypropylene, oxy-1,2-butylene,oxy-1,4-butylene or a co-polymer thereof.

Examples of aliphatic polyamines include, but are not limited toethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine(TETA), trimethyl hexane diamine (TMDA), hexamethylenediamine (NMDA),N-(2-aminoethyl)-1,3-propanediamine (N₃-Amine),N,N′-1,2-ethanediylbis-1,3-propanediamine (N₄-amine), anddipropylenetriamine. Examples of arylaliphatic polyamines include, butare not limited to m-xylylenediamine (mXDA), and p-xylylenediamine.Examples of cycloaliphatic polyamines include, but are not limited to1,3-bisaminocyclohexylamine (1,3-BAC), isophorone diamine (IPDA), and4,4′-methylenebiscyclohexanamine. Examples of aromatic polyaminesinclude, but are not limited to m-phenylenediamine,diaminodiphenylmethane (DDM), and diaminodiphenylsulfone (DDS). Examplesof heterocyclic polyamines include, but are not limited toN-aminoethylpiperazine (NAEP), and 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane. Examples of polyalkoxypolyamineswhere the alkoxy group is an oxyethylene, oxypropylene,oxy-1,2-butylene, oxy-1,4-butylene or a co-polymer thereof include, butare not limited to 4,7-dioxadecane-1,10-diamine,1-propanamine,2,1-ethanediyloxy))bis(diaminopropylated diethyleneglycol) (ANCAMINE® 1922A); poly(oxy(methyl-1,2-ethanediyl)),alpha-(2-aminomethylethyl)omega-(2-aminomethylethoxy) (JEFFAMINE® D-230,D-400); triethyleneglycoldiamine and oligomers (JEFFAMINE® XTJ-504,JEFFAMINE® XTJ-512),poly(oxy(methyl-1,2-ethanediyl)),alpha,alpha′-(oxydi-2,1-ethanediyl)bis(omega-(aminomethylethoxy))(JEFFAMINE® XTJ-511); bis(3-aminopropyl)polytetrahydrofuran 350;bis(3-aminopropyl)polytetrahydrofuran 750;poly(oxy(methyl-1,2-ethanediyl)), a-hydro-w-(2-aminomethylethoxy) etherwith 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (JEFFAMINE® T-403), anddiaminopropyl dipropylene glycol.

The adducts may have a viscosity of 500 mPa·s t650,000 mPa·s. Theadducts may have a hydrogen equivalent weight of 60 grams per equivalent(g/eq) to 200 g/eq. The viscosity and/or the hydrogen equivalent weightcan depend, at least in part, on an initial molar ratio of the epoxycompound and the first amine. However, embodiments are not limited tothese values and other viscosities and/or hydrogen equivalent weightsare possible. For some applications the adducts may have a viscosity of3,000 mPa·s to 7,000 mPa·s.

As mentioned above, the hardener component includes a Mannich base. AMannich base is a reaction product of the reaction of an aldehyde, aphenol compound, and a second amine. An example of the aldehydeincludes, but is not limited to, formaldehyde. The second amine can beindependently selected from the same amines and/or groups as the firstamine, as discussed herein.

For one or more of the embodiments, the phenol compound used to form theMannich bases includes monophenols, for example, phenol, ortho-, meta-or para-cresol, the isomeric xylenols, para-tertiary-butylphenol,para-nonylphenol, α-naphthol, and β-naphthol and combinations thereof.The phenol compound can include di- and poly-phenols such as resorcinol,hydroquinone, 4,4′-dioxydiphenyl, 4,4′-dioxydiphenylether,4,4′-dioxydiphenylsulfone, 4,4′-dioxydiphenylmethane, bisphenol A, andcombinations thereof. The phenol compound can include condensationproducts of phenol and formaldehyde, known as novolacs.

The Mannich base helps provide that the curable composition has a rapidcure time. Herein, the rapid cure time refers to a cure time that is 120minutes or less. For example, the rapid cure time can be from 5 minutesto 120 minutes when the curable composition is cured at a temperature offrom −5° C. to 50° C. Additionally, the Mannich bases help providedesirable mechanical strength and hardness properties, as well asdesirable chemical resistance properties.

For one or more of the embodiments, the Mannich base is from 10 to 90weight percent the total weight of the hardener component, such that theweight percent of the adduct and the weight percent of the Mannich baseequal one hundred weight percent of the hardener component. Examples ofphenols and/or amines that are useful for one or more of the embodimentscan be found in Tramontini, Maurilio, “Advances in the Chemistry ofMannich Bases.” Syntheses, 1973: 703-775, incorporated herein byreference.

The Mannich bases may have a viscosity of 100 mPa·s to 10,000 mPa·s; ahydrogen equivalent weight of 60 g/eq to 200 g/eq; and a pot life offrom 5 minutes to 60 minutes at 25° C. The viscosity, the hydrogenequivalent weight, and/or the pot life of the Mannich base can depend,at least in part, on an initial molar ratio of the epoxy compound andthe second amine. However, embodiments are not limited to these values,and other values for viscosity, hydrogen equivalent weight and/or potlife of the Mannich base are possible. For some applications the Mannichbases may have a viscosity of 3,000 mPa·s to 7,000 mPa·s.

For one or more of the embodiments, the curable compositions do notinclude volatile organic compounds. The curable compositions may have aviscosity of from 1,000 mPa·s to 10,000 mPa·s at 25° C. The curablecompositions may have a pot life of from 15 minutes to 60 minutes at 25°C. In some embodiments, the curable compositions may have a pot life offrom 15 minutes to 90 minutes at 25° C. However, embodiments are notlimited to these values, and other values for viscosity and/or pot lifeof the curable composition are possible. For some applications thecurable compositions may have a viscosity of 2,000 mPa·s to 8,000 mPa·s.

For one or more of the embodiments, the curable compositions can includean additive. Examples of the additive include, but are not limited to, amodifier such as a non-reactive modifier; an accelerator, a flow controladditive such as a solvent or an anti-sag agent, a pigment, areinforcing agent, a filler, an elastomer, a stabilizer, an extender, aplasticizer, and a flame retardant, depending upon the application. Forone or more of the embodiments the curable compositions can include anadditional curing agent. The additional curing agent can be selectedfrom the group consisting of an amine, an anhydride, a carboxylic acid,a phenol, a thiol, and combinations thereof.

The curable compositions are advantageous as a coating. The coating caninclude a cured composition that is obtained by a reaction of the resincomponent and the hardener component as discussed herein. The curablecompositions can be applied to a substrate and cured thereon. Forexample, the substrate can be metal, plastic, fiberglass, or anothermaterial that the curable compositions can bond to. The curablecompositions can be applied to the substrate by various procedures, suchas dipping, spraying, rolling, or another procedure. The coating on thesubstrate can be useful for forming articles, such as coated containersthat are employed to hold liquids. For example, embodiments of thecoated containers may include a potable water container and/or a winefermentation tank/container. For some applications, the coating on thesubstrate may be from 0.2 millimeters (mm) to 5 mm thick. However,embodiments are not limited to this value, and other values for coatingthickness are possible.

For one or more of the embodiments, the curable compositions can becured to produce a cured composition having a hardness of from 76 to 84on a Shore D hardness scale. The hardness can be determined by ASTM D2240. For one or more of the embodiments, the cured composition has aglass transition temperature of from 40° C. to 80° C. However,embodiments are not limited to these values, other hardness values onthe Shore D hardness scale and/or glass transition temperatures arepossible.

EXAMPLES

The following Examples of curable compositions including a resincomponent, a reactive diluent, and a hardener component are given toillustrate, but not limit, the scope of this disclosure. Unlessotherwise indicated, all parts and percentages are by weight. Unlessotherwise specified, all instruments and chemicals used are commerciallyavailable.

Materials

Isophorone diamine (IPDA), available from Evonik Industries.

Para-tertiary-butylphenol (PTBP), available from SI Group®, Inc.

Formaldehyde, available from Brenntag.

D.E.R.™ 331, (aromatic epoxy compound), available from The Dow ChemicalCompany.

meta-Xylenediamine (MXDA), available from Mitsubishi Gas ChemicalCompany, Inc.

Diethylene triamine (DETA), available from Delamine B.V.

Trimethyl hexane diamine (TMDA), available from Evonik Industries.

JEFFAMINE® D-230 Polyoxypropylenediamine (D-230), available fromHuntsman International LLC.

ortho-Cresyl(mono)glycidyether (oC-MGE), available from UPPC GmbH.

Styrenated phenol (Sanko SP(SP)), (non-reactive modifier), availablefrom Sanko Europe GmbH.

Diisopropylnaphthalene (Ruetasolv DI), (non-reactive modifier),available from RKS GmbH.

POLYPOX® E 403, (aromatic epoxy compound), available from The DowChemical Company.

POLYPOX® VE 101592, (reactive diluent of polymeric glycidyl ether thatis a triglycidyl ether of trimethylolpropan octadeca ethoxilate),available from UPPC GmbH.

POLYPOX® IH 7009, (polyamine), available from UPPC GmbH.

DOWANOL® TpnB (TpnB), (Tripropylene glycol n-butyl ether), (non-reactivemodifier) available from The Dow Chemical Company.

NOVARES LS 500 (LS 500), (non-reactive modifier), available fromRuetgers VfT.

UCAR™ Filmer IBT (IBT), (non-reactive modifier), Chemical AbstractsService (CAS) registry number 25265-77-4, available from The DowChemical Company.

Acetic acid, analytical grade, available from Merck KGaA.

Ethanol, analytical grade, available from Merck KGaA.

Artificial wine, mixture of 3 volume percent (vol %) vinegar having a 5weight percent (wt %) acetic acid content, 14 vol % ethanol, 83 vol %water.

Sulfuric acid, analytical grade, available from Merck KGaA.

Sodium hydroxide, analytical grade, available from Merck KGaA.

B.P.G 5b, mixture of 48 vol % methanol, analytical grade, available fromMerck KGaA, 48 vol % isopropanol, analytical grade, available from MerckKGaA, and 4 vol % water.

Gasoline, available from Esso (Exxon).

Xylene, analytical grade, available from Merck KGaA.

Methyl isobutyl ketone (MIBK), analytical grade, available from MerckKGaA.

Deionized water.

Mannich Base Preparation

Mannich bases 1 through 10 were prepared as follows: A three-neckedflask equipped with a mechanical stirrer, a heating jacket, athermometer, and a Liebig type horizontal cooler, was used to preparethe Mannich bases. IPDA was first added to the flask. Then, PTBP wasdissolved in the IPDA at 90° C. Twenty wt % formaldehyde solution wasadded dropwise to the flask while water, which was introduced from theformaldehyde solution, was simultaneously removed via heating at atemperature of from 100° C. to 135° C. with a pressure of about 101.3kPa. The resultant product was cooled to 90° C. when the addition of theformaldehyde solution was completed. Subsequently, the resultant productwas maintained at 90° C. for 5 minutes (min) and a vacuum of 100millibar (mbar) was applied. Then, the product was heated to 135° C. Theproduct was distilled to a water content below 0.5 wt %. Thereafter, theproduct was cooled to 40° C. Table 1 shows components, and theirrespective amounts in moles, used to prepare the respective Mannichbases. Table 1 also shows the grams of water distilled during thepreparation of the respective Mannich bases 1-10.

TABLE 1 Mannich Mannich Mannich Mannich Mannich Mannich Mannich MannichMannich Mannich COMPONENT Base 1 Base 2 Base 3 Base 4 Base 5 Base 6 Base7 Base 8 Base 9 Base 10 PTBP 1.12 0.37 0.37 0.75 1.12 0.75 0.75 1.121.12 0.9 (moles) IPDA 0.7 1.4 1.4 1.4 1.4 1.4 0.7 1.4 1.4 1.4 (moles)Formaldehyde 0.35 0.7 0.35 0.35 0.35 0.7 0.35 0.7 1.05 0.6 (moles)Distilled 42.81 91.6 46.1 47.2 47.9 91.65 95.13 95.12 141.88 77.78 water(grams)

Various properties of Mannich bases 1 through 10 were determined and theresults are shown in Table 2; including the theoretical amine value ofthe respective Mannich bases in milligrams potassium hydroxide per gram(mg KOH/g) as determined by the constituents of the respective Mannichbases; the measured amine value of the respective Mannich bases in mgKOH/g as determined according to DIN 16945; the water content as a wt %of the respective Mannich bases; the viscosity as mPa·s of therespective Mannich bases at 25° C.; the viscosity as mPa·s of therespective Mannich bases at 40° C.; the refractive index of therespective Mannich bases at 25° C.; the pot life of the respectiveMannich bases in minutes, wherein the respective Mannich bases are mixedwith D.E.R.™ 331 (1 epoxy equivalent: 1 amine equivalent); and thehydrogen equivalent weight as grams per equivalent (g/eq) of respectiveMannich base as determined by the constituents of the respective Mannichbases.

TABLE 2 Mannich Mannich Mannich Mannich Mannich Mannich Mannich MannichMannich PROPERTY Mannich Base 1 Base 2 Base 3 Base 4 Base 5 Base 6 Base7 Base 8 Base 9 Base 10 Theoretical 272 524 531 447 386 441 336 382 378405 amine value (mg KOH/g) Measured 272 535 525 455 390 439 340 386 380398 amine value (mg KOH/g) Water 0.35 0.50 0.40 0.36 0.50 0.22 0.40 0.27— — content (wt %) Viscosity — 13000 500 1600 5600 32000 — 70000 — 16500at 25° C. (mPa · s) Viscosity 30000 2100 130 310 630 3500 10700 6600125000 2000 at 40° C. (mPa · s) Refractive 1.5274 1.5137 1.5056 1.51111.5166 1.5183 1.5233 1.5216 1.5267 1.5172 index at 25° C. Pot life 25168 83 43 27 64 31 44 129 44 (minutes) Hydrogen 121 62 57 68 78 74 96 8492 79 equivalent weight (g/eq)

Adduct Preparation

Adducts 1 through 8 were prepared as follows: Amine was added to a flaskand flask contents were heated to a reaction temperature of 90° C. Theflask contents were heated to a reaction temperature of 140° C. whenD-230 was included. Epoxy compound was then added dropwise to the flaskwhile stirring. The flask contents were maintained to within ±5° C. ofthe reaction temperature. The flask contents were cooled to 40° C. onehour after the addition of the epoxy compound was completed. Table 3shows the components, and their respective amounts in moles, used toprepare the respective adducts.

TABLE 3 COMPONENT Adduct 1 Adduct 2 Adduct 3 Adduct 4 Adduct 5 Adduct 6Adduct 7 Adduct 8 D.E.R. ™ 331 1 1.28 0.75 0.7 0.75 — — — (moles) oC-MGE— — — — — —  1.25 — (moles) ptBP-MGE — — — — —  1.25 —  1.25 (moles)MXDA 4 — — — — — — — (moles) DETA — 5.11 — — — — — — (moles) TMDA — —3   — — — — — (moles) D-230 — — —  2.79 — 2.5 2.5 — (moles) IPDA — — — —3   — — 2.5 (moles)

Various properties of adducts 1 through 8 were determined and theresults are shown in Table 4, including the viscosity as mPa·s of therespective adducts at 25° C.; the viscosity as mPa·s of the respectiveadducts at 50° C.; and the hydrogen equivalent weight as grams perequivalent (g/eq) of respective adduct.

TABLE 4 PROPERTY Adduct 1 Adduct 2 Adduct 3 Adduct 4 Adduct 5 Adduct 6Adduct 7 Adduct 8 Viscosity 20500 7000 1700 2300 — 211 150 3460 at 25°C. (mPa · s) Viscosity — — — — 29000 — — — at 50° C. (mPa · s) Hydrogen  65 43.5  64  102 74 109 101  82 equivalent weight (g/eq)

Hardener Preparation

Mannich base 5 and Mannich base 8 were combined with some of thepreviously prepared adducts to provide hardener components 1 through 12,as indicated by Table 5. Table 5 shows the wt % of Mannich base 5 andthe wt % of Mannich base 8 used with the respective hardener components.Table 5 also shows the wt % of non-reactive modifiers Sanko SP andRuetasolv DI used with the respective hardener components.

TABLE 5 COMPONENT Hard- Hard- ener ener Hardener Hardener HardenerHardener Hardener Hardener Hardener Hardener Hardener Hardener Com- Com-Com- Com- Com- Com- Com- Com- Com- Com- Com- Com- ponent ponent ponentponent 1 ponent 2 ponent 3 ponent 4 ponent 5 ponent 6 ponent 7 ponent 8ponent 9 10 11 12 Mannich 50% 50% 50% 50% — — — 50% 33% 40% 40% 40% base5 (wt %) Mannich — — — — 50% 50% 50% — — — — — base 8 (wt %) AdductAdduct 1 Adduct 2 Adduct 3 Adduct 4 Adduct 2 Adduct 3 Adduct 4 Adduct 1Adduct 3 Adduct Adduct Adduct 3 (wt %) (50%) (50%) (50%) (50%) (50%)(50%) (50%) (25%) (33%) 3 4 (20%) (40%) (40%) Adduct — — — — — — —Adduct 3 — — — Adduct 1 (wt %) (25%) (20%) Sanko SP — — — — — — — — 33%— — — (non- reactive modifier) (wt %) Ruetasolv — — — — — — — — — 20%20% 20% DI (non reactive modifier) (wt %)

Various properties of the hardener components 1 through 12 weredetermined and the results are shown in Tables 6A-6D. Table 6A shows thehydrogen equivalent weight as grams per equivalent (g/eq) of respectivehardener components; the viscosity as mPa·s of the respective hardenercomponents at 25° C.; and the viscosity as mPa·s of the respectivehardener components at 40° C. Table 6B shows the grams of the respectivehardener components mixed with 100 grams of D.E.R.™ 331; and the potlife in minutes of the mixtures. Table 6C shows the grams of therespective hardener components mixed with 100 grams of POLYPOX® E 403;and the pot life in minutes of the mixtures. Table 6D shows the grams ofthe respective hardener components mixed with 100 grams of D.E.R.™331/POLYPOX® VE 101592 (80 wt %:20 wt %); and the pot life in minutes ofthe mixtures of Row 6.8.

TABLE 6A Hard- Hard- Hard- ener ener ener Hardener Hardener HardenerHardener Hardener Hardener Hardener Hardener Hardener Com- Com- Com-Com- Com- Com- Com- Com- Com- Com- Com- Com- ponent ponent ponentPROPERTY ponent 1 ponent 2 ponent 3 ponent 4 ponent 5 ponent 6 ponent 7ponent 8 ponent 9 10 11 12 Hydrogen 71 56 70 88 57 73 92 71 105 87 11088 equivalent weight (g/eq) Viscosity 9300 4700 2360 2900 11800 59005900 4550 13700 700 835 1200 at 25° C. (mPa · s) Viscosity 1600 1100 565630 2350 1200 1100 — — — — — at 40° C. (mPa · s)

TABLE 6B Hard- Hard- Hard- ener ener ener Hardener Hardener HardenerHardener Hardener Hardener Hardener Hardener Hardener Com- Com- Com-Com- Com- Com- Com- Com- Com- Com- Com- Com- ponent ponent ponentPROPERTY ponent 1 ponent 2 ponent 3 ponent 4 ponent 5 ponent 6 ponent 7ponent 8 ponent 9 10 11 12 Grams of 39 31 39 48 31 40 51 — — — — —hardener component per 100 grams D.E.R. ™ 331 Pot life of 35 28 34 69 3342 103 — — — — — hardener component + resin mixture (minutes)

TABLE 6C Hard- Hard- Hard- Hard- ener ener ener ener Hardener HardenerHardener Hardener Hardener Hardener Hardener Hardener Com- Com- Com-Com- Com- Com- Com- Com- Com- Com- Com- Com- ponent ponent ponent ponentPROPERTY ponent 1 ponent 2 ponent 3 ponent 4 ponent 5 ponent 6 ponent 7ponent 8 9 10 11 12 Grams of — — 36 46 — — — 37 55 45 57 46 hardenercomponent per 100 grams POLYPOX ® 403 Pot life of — — 48 135 — — — 44 2767 235 63 hardener component + resin mixture (minutes)

TABLE 6D Hard- Hard- Hard- Hard- ener ener ener ener Hardener HardenerHardener Hardener Hardener Hardener Hardener Hardener Com- Com- Com-Com- Com- Com- Com- Com- Com- Com- Com- Com- ponent ponent ponent ponentPROPERTY ponent 1 ponent 2 ponent 3 ponent 4 ponent 5 ponent 6 ponent 7ponent 8 9 10 11 12 Grams of — — 33 41 — — — 33 49 — — — hardenercomponent per 100 grams of an 80 wt %:20 wt % blend of D.E.R. ™ 331/POLYPOX ® VE 101592 Pot life of — — 51 149 — — — 48 29 — — — hardenercomponent + resin mixture (minutes)

Examples 1-17

The aromatic resin compound D.E.R.™ 331 and the polymeric glycidyl etherPOLYPOX® VE 101592 were mixed to provide a resin component that was thenmixed with a Mannich base, an adduct(s) and, for some Examples, anon-reactive modifier to provide curable compositions shown as Examples1 through 17 of Table 7A. In each Example there was 100 grams of resincomponent total. Table 7A shows the wt % of the resin components foreach Example. The resin components were mixed with a mass of Mannichbase, adduct(s), and non-reactive modifier(s) as shown in Table 7A.Table 7A shows the wt % of each respective Mannich base, adduct(s), andnon-reactive modifier(s) for the total mass thereof.

TABLE 7A POLYPOX ® D.E.R. ™ VE 101592 331 (reactive Mannich (aromaticdiluent Grams of base Adduct Non-reactive modifier epoxy of polymericMannich Mannich Adduct Adduct Adduct Sanko Ruetasolv UCAR ™ DOWANOL ®compound) glycidyl ether) base + base 5 1 3 4 SP DI Filmer IBT TpnBEXAM- Wt % of resin adduct(s) + Wt % PLE # component modifier(s) Mannichbase/adduct(s)/non-reactive modifier(s) Example 1 80 20 33 50 — 50 — — —— — Example 2 80 20 33 50 50 — — — — — — Example 3 80 20 50 33.3 33.3 —— 33.3 — — — Example 4 80 20 49 33.3 — 33.3 — 33.3 — — — Example 5 80 2033 50 25 25 — — — — — Example 6 80 20 50 33.3 16.7 16.7 — 33.3 — — —Example 7 80 20 41 40 — 40 — — — 20 — Example 8 80 20 55 30 — 30 — — —40 — Example 9 80 20 41 40 — 40 — — — — 20 Example 80 20 55 30 — 30 — —— — 40 10 Example 80 20 62 33.3 — — 33.3 33.3 — — — 11 Example 80 20 5041 — — 41 — 18 — — 12 Example 80 20 52 40 — — 40 — — 20 — 13 Example 8020 69 30 — — 30 — — 40 — 14 Example 80 20 52 40 — — 40 — — — 20 15Example 80 20 57 30 — — 30 — — — 40 16 Example 80 20 41 50 — — 50 — — —— 17

Comparative Examples A-Y

The aromatic epoxy compound POLYPOX® E 403 was mixed with a Mannichbase, an adduct (s) and, for some Examples, a non-reactive modifier toprovide curable compositions shown as Comparative Examples A-Y of Table7B. In each Comparative Example there was 100 grams of aromatic epoxycompound. Table 7B shows the wt % of the resin component for eachComparative Example. The resin components were mixed with a mass ofMannich base, adduct(s), and non-reactive modifier(s) as shown in Table7B. Table 7B shows the wt % of each respective Mannich base, adduct(s),and non-reactive modifier(s) for the total mass thereof.

TABLE 7B POLYPOX ® Mannich E 403 Grams of base Adduct Non-reactivemodifier (aromatic epoxy Mannich Mannich Adduct Adduct Ruetasolvcompound) base + base 5 1 Adduct 2 Adduct 3 4 SP LS 500 DI IBT TpnBCOMPARATIVE Wt % of resin adduct(s) + Wt % EXAMPLE # componentmodifier(s) Mannich base/adduct(s)/non-reactive modifier(s) Comparative100 36 50 — — 50 — — — — — — Example A Comparative 100 29 50 — 50   — —— — — — — Example B Comparative 100 37 50 50 — — — — — — — — Example CComparative 100 55 33.3 33.3 — — — 33.3 — — — — Example D Comparative100 44 33.3 — 33.3 — — 33.3 — — — — Example E Comparative 100 55 33.3 —— 33.3 — 33.3 — — — — Example F Comparative 100 37 50 25 — 25 — — — — —— Example G Comparative 100 58 33.3 16.7 — 16.7 — 33.3 — — — — Example HComparative 100 52 33.3 — 16.7 16.7 — 33.3 — — — — Example I Comparative100 55 31.7 — 15.8 15.8 — 31.7 5 — — — Example J Comparative 100 60 31.7— — 31.7 — 31.7 5 — — — Example K Comparative 100 49 31.7 — 31.7 — — — 5— — — Example L Comparative 100 45 40 — — 40 — — — 20 — — Example MComparative 100 46 40 20 — 20 — — — 20 — — Example N Comparative 100 4540 — — 40 — — — — 20 — Example O Comparative 100 61 30 — — 30 — — — — 40— Example P Comparative 100 45 40 — — 40 — — — — — 20 Example QComparative 100 61 30 — — 30 — — — — — 40 Example R Comparative 100 4650 — — — 50 — — — — — Example S Comparative 100 69 33.3 — — — 33.3 33.3— — — — Example T Comparative 100 57 33.3 — — — 40 — — 20 — — Example UComparative 100 57 40 — — — 40 — — — 20 — Example V Comparative 100 7630 — — — 30 — — — 40 — Example W Comparative 100 57 40 — — — 40 — — — —20 Example X Comparative 100 76 30 — — — 30 — — — — 40 Example Y

Properties of the Examples of Table 7A and Comparative Examples of Table7B were determined, and the results are shown in Tables 8A, 8B, 9A, and9B. These Tables show the viscosity of the hardener component andnon-reactive modifier, if any, in mPa·s at 25° C., and the Shore Dhardness determined by ASTM D 2240, after curing for a number of hours(h) at a particular relative humidity. The curing at 23° C. occurred at50 percent relative humidity, the curing at 13° C. occurred at 80percent relative humidity, and the curing at 7° C. occurred at 65percent relative humidity.

TABLE 8A Viscosity of Shore D Shore D the hardener hardness hardnesscomponent + Shore D hardness after after non-reactive after curingcuring curing modifier at 23° C. at 13° C. at 7° C. EXAMPLE # (mPa · s)4.5 h 5.0 h 6.0 h 6.5 h 7.0 h 8.0 h 24 h 8.0 h 24 h 8.0 h 24 h Example 12360 — 13 — 28 — 45 76 — 65 — 75 Example 2 9300 — 22 — 46 — 62 78 — 71 —71 Example 3 — 32 — 64 — 70 71 78 37 74 38 72 Example 4 13700 — — 37 —49 56 74 25 66 28 68 Example 5 — — — 23 — 40 56 76 — 66 — 64 Example 6 —23 — 55 — 60 61 77 33 56 48 70 Example 7 1300 — — — — — 10 68 — 48 — 30Example 8 620 — — — — — — 45 — 21 — 20 Example 9 585 — — — — — 10 63 —38 — 25 Example 175 — — — — — — 25 — 10 — — 10

TABLE 8B Viscosity of Shore D Shore D the hardener hardness hardnesscomponent + Shore D hardness after after non-reactive after curingcuring curing COMPARATIVE modifier at 23° C. at 13° C. at 7° C. EXAMPLE# (mPa · s) 4.5 h 5.0 h 6.0 h 6.5 h 7.0 h 8.0 h 24 h 8.0 h 24 h 8.0 h 24h Comparative 2360 — — 16 — 35 58 79 — 74 — 71 Example A Comparative4700 20 — 44 — 55 68 79 — 72 10 74 Example B Comparative 9300 13 — 43 —55 72 79 — 70 13 73 Example C Comparative — — 59 70 — — 74 74 35 70 4569 Example D Comparative — — 53 65 — — 70 74 23 72 43 73 Example EComparative 13700 — 38 53 — — 64 72 23 73 18 72 Example F Comparative4500 — — 43 — 61 63 78 — 67 — 75 Example G Comparative — 49 — 66 — 70 7279 26 72 24 73 Example H Comparative — 50 — 65 — 72 73 78 27 75 38 75Example I Comparative — 40 — 61 — 63 65 76 14 69 15 68 Example JComparative — 27 — 50 — 57 58 76 13 63 20 65 Example K Comparative — 53— 69 — 72 73 80 25 75 18 77 Example L Comparative 700 — — — — 18 25 73 —56 — 61 Example M Comparative 1200 — — — — 32 41 82 — 68 — 71 Example NComparative 1300 — — — — 15 25 73 — 62 — 58 Example O Comparative 620 —— — — — — 47 — 28 — 23 Example P Comparative 585 — — — — — 20 68 — 48 —54 Example Q Comparative 175 — — — — — — 28 — 10 — 11 Example R

TABLE 9A Viscosity of the hardener Shore D component + Shore D hardnessShore D hardness hardness non-reactive after curing after curing aftercuring modifier at 23° C. at 13° C. at 7° C. EXAMPLE # (mPa · s) 16 h 18h 24 h 48 h 16 h 18 h 24 h 48 h 18 h 24 h 48 h Example — 56 63 67 74 2328 45 72 24 34 64 11 Example 910 17 22 38 71 — — — 38 — — 28 12 Example1300  16 20 39 67 — — — 38 — — 28 13 Example 550 — — 14 35 — — — — — — —14 Example 600 — 12 25 60 — — — 20 — — 18 15 Example 155 22 25 49 73 — —— 48 — — 22 16

TABLE 9B Viscosity of the hardener Shore D component + Shore D hardnessShore D hardness hardness non-reactive after curing after curing aftercuring COMPARATIVE modifier at 23° C. at 13° C. at 7° C. EXAMPLE # (mPa· s) 16 h 18 h 24 h 48 h 16 h 18 h 24 h 48 h 18 h 24 h 48 h Comparative2900 58 62 65 80 — — 20 71 — 20 71 Example S Comparative — 61 63 73 7825 25 52 70 — 42 67 Example T Comparative 835 — 25 48 74 — —  9 53 —  952 Example U Comparative 1300 22 25 49 73 — — — 48 — — 22 Example VComparative 550 — — 12 38 — — — 12 — — — Example W Comparative 600 — 1430 67 — — — 24 — — 12 Example X Comparative 155 — — — 20 — — — — — — —Example Y

The Tg of some Examples and Comparative Examples, as described above,was measured and the results are shown in Tables 10A and 10B. TheExamples and Comparative Examples were thermoanalyzed with a MettlerToledo DSC822, available from Mettler-Toledo Inc. The active glasstransition temperature (Tg_(A)) was measured in the range of 20° C. to120° C. The potential glass transition temperature (Tg_(P)) was measuredafter a 10 minute postcuring at 180° C. in the range of 20° C. to 130°C. following Deutsches Institut für Normung (DIN), or German Institutefor Standardization DIN 65467, heating rate 15 kelvin/minute.

TABLE 10A Tg_(A) Tg_(P) EXAMPLE # (° C.) (° C.) Example 1 54.9 63.0Example 2 53.9 64.1 Example 3 48.9 59.5 Example 5 55.3 66.4 Example 647.8 54.2 Example 11 43.3 51.4 Example 12 41.7 51.0 Example 13 40.4 49.8Example 15 42.1 55.2

TABLE 10B COMPARATIVE Tg_(A) Tg_(P) EXAMPLE # (° C.) (° C.) Comparative59.5 72.7 Example A Comparative 61.8 81.5 Example B Comparative 52.357.2 Example D Comparative 55.9 62.2 Example E Comparative 53.0 55.1Example F Comparative 59.4 79.8 Example G Comparative 51.6 55.4 ExampleH Comparative 53.9 58.3 Example I Comparative 51.3 58.5 Example MComparative 47.5 57.2 Example O Comparative 44.8 58.1 Example QComparative 39.1 49.3 Example R Comparative 57.0 65.7 Example SComparative 46.9 52.1 Example T Comparative 39.5 57.0 Example UComparative 41.2 52.2 Example X

The chemical resistance of POLYPOX® E 403 mixed with POLYPOX® IH 7009 (1epoxy equivalent to 1 amine equivalent), herein Comparative Example Z,Comparative Example A, and Comparative Example M were evaluated by ShoreD hardness testing (ASTM D 2240) and determination of a percent changein hardness on the Shore D hardness scale. Comparative Examples A and Meach have a hardener component that includes the Mannich base and adductas disclosed herein, in contrast to Comparative Example Z. A relativelylesser percent change in hardness indicated a greater chemicalresistance and a relatively greater percent change in hardness indicateda lower chemical resistance. Various solutions were used for thechemical resistance tests including a five wt % acetic acid solution, afifteen wt % ethanol solution, and artificial wine. The Shore Dhardness, prior to exposure to the solutions, was measured for each ofthe cured compositions, and is shown in Table 11 as initial hardness.

A sample of each of Comparative Example Z, Comparative Example A, andComparative Example M was exposed to the solutions for 168 h by placinga cotton pad that is saturated with the solution on the sample andcovering the pad and sample. After 24 h of exposure, 48 h of exposure,and 168 h of exposure the Shore D hardness of the samples was measured.The Shore D hardness measurements are shown in Table 11. The percentchange in Shore D hardness, as shown as percent % A Shore D hardness inTable 11, was determined with the initial hardness and the finalhardness that is the hardness after 168 h of exposure to the solutionsto the initial hardness. The percent change in Shore D hardness wascalculated as (1−(final hardness/initial hardness))*100, where anegative percent change in hardness indicated a greater value forinitial hardness than final hardness.

TABLE 11 Acetic Acid Ethanol Artificial Wine Initial % Δ % Δ % ΔCOMPARATIVE Shore D Shore D Shore D Shore D EXAMPLE # Hardness 24 h 48 h168 h Hardness 24 h 48 h 168 h Hardness 24 h 48 h 168 h HardnessComparative 81 66 63 55 −32.10 79 79 78 −3.70 77 75 77 −4.90 Example ZComparative 78 77 75 74 −5.10 79 79 77 −1.30 77 77 77 −1.30 Example AComparative 79 74 74 72 −8.86 77 77 78 −1.27 77 77 78 −1.27 Example M

The data in Table 11 shows that both Comparative Example A andComparative Example M have improved chemical resistance, shown by therelative percent change in hardness after exposures to acetic acid,ethanol, and artificial wine for 168 h, as compared to ComparativeExample Z.

The chemical resistance of a mixture of 80 wt % D.E.R.™ 331 and 20 wt %POLYPOX® VE 101592 combined with POLYPOX® IH 7009 (1 epoxy equivalent to1 amine equivalent), herein Comparative Example AA, Example 17, andExample 1 as described above, was evaluated with chemical exposures tovarious solutions including a twenty wt % sulfuric acid solution, atwenty wt % sodium hydroxide solution, B.P.G. 5b, a five wt % aceticacid solution, a ten wt % acetic acid, gasoline, xylene, MIBK, a fifteenwt % ethanol solution, and artificial wine. The Shore D hardness, priorto exposure to the solutions for each of the cured compositions, wasmeasured and is shown in Table 12 as initial Shore D hardness.

Each sample was exposed to the solutions for a period of time as shownin Table 12; Shore D hardness measurements were taken and the resultsare shown in Table 12; and the percent change in Shore D hardness, asdescribed above, was determined and is shown in Table 12.

TABLE 12 Comparative Example Example Example AA 17 1 (Initial (Initial(Initial Shore D Shore D Shore D hardness hardness hardness SOLUTION 81)81) 82) Sulfuric acid Shore D 76 78 82 hardness after 24 h Shore D 76 7881 hardness after 48 h Shore D 71 75 81 hardness after 168 h % Δ −12.35−7.41 −1.22 Shore D Hardness Sodium Shore D 81 81 82 hydroxide hardnessafter 24 h Shore D 81 81 82 hardness after 48 h Shore D 81 80 81hardness after 168 h % Δ 0.00 −1.23 −1.22 Shore D Hardness B.P.G. 5bShore D 71 71 74 hardness after 24 h Shore D 67 69 72 hardness after 48h Shore D 61 62 69 hardness after 168 h % Δ −24.69 −23.46 −15.85 Shore DHardness Acetic acid 5% Shore D 63 70 77 hardness after 24 h Shore D 5667 75 hardness after 48 h Shore D 42 60 69 hardness after 168 h % Δ−48.15 −25.93 −15.85 Shore D Hardness Acetic acid Shore D 56 68 72 10%hardness after 24 h Shore D 48 62 69 hardness after 48 h Shore D 28 5158 hardness after 168 h % Δ −65.43 −37.04 −29.27 Shore D HardnessGasoline Shore D 82 80 80 hardness after 24 h Shore D 81 80 80 hardnessafter 48 h Shore D 81 79 80 hardness after 168 h % Δ 0.00 −2.47 −2.44Shore D Hardness Xylene Shore D 70 65 69 hardness after 24 h Shore D 6760 68 hardness after 48 h Shore D 59 50 61 hardness after 168 h % Δ−27.16 −38.27 −25.61 Shore D Hardness Methyl isobutyl Shore D 75 65 67ketone hardness after 24 h Shore D 73 60 67 hardness after 48 h Shore D65 54 59 hardness after 168 h % Δ −19.75 −33.33 −28.05 Shore D HardnessEthanol 15% Shore D 79 78 81 hardness after 24 h Shore D 78 78 80hardness after 48 h Shore D 76 79 80 hardness after 168 h % Δ −6.17−2.47 −2.44 Shore D Hardness Artificial wine Shore D 78 78 82 hardnessafter 24 h Shore D 77 78 82 hardness after 48 h Shore D 76 79 81hardness after 168 h % Δ −6.17 −2.47 −1.22 Shore D Hardness

The data in Table 12 shows that both Example 17 and Example 1 haveimproved chemical resistance, shown by the relative percent changes inhardness after exposures to sulfuric acid, B.P.G. 5b, five wt % aceticacid solution, ten wt % acetic acid solution, fifteen wt % ethanolsolution, and artificial wine for 16811, as compared to ComparativeExample AA.

1. A curable composition comprising: a resin component that includes; anepoxy compound that is selected from the group consisting of aromaticepoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds,and combinations thereof; and a reactive diluent that includes atriglycidyl ether of trimethylolpropan octadeca ethoxilate; and ahardener component that includes; an adduct formed from the combinationof the epoxy compound and a first amine selected from the groupconsisting of arylaliphatic polyamines, cycloaliphatic polyamines, andcombinations thereof; and a Mannich base formed from a reaction offormaldehyde, a phenol compound, and a second amine selected from thegroup consisting of arylaliphatic polyamines, cycloaliphatic polyamines,and combinations thereof.
 2. The curable composition of claim 1, whereinthe phenol compound is selected from the group consisting ofmonophenols, diphenols, polyphenols, and combinations thereof.
 3. Thecurable composition of claim 2, wherein the epoxy compound is anaromatic epoxy compound; the first amine is selected from the groupconsisting of isophorone diamine, m-xylylenediamine, and combinationsthereof; the second amine is isophorone diamine; and the phenol compoundis para-tertiary-butylphenol.
 4. The curable composition of claim 1,wherein the reactive diluent is less than 60 weight percent of the totalweight of the resin component; the adduct is from 10 weight percent to90 weight percent of the hardener component; and the Mannich base isfrom 10 to 90 weight percent of the hardener component, such that theweight percent of the adduct and the weight percent of the Mannich baseequal one hundred weight percent of the hardener component.
 5. Thecurable composition of claim 1, wherein the Mannich base has a viscosityof from 100 mPa·s to 10,000 mPa·s at 25° C. and a hydrogen equivalentweight of from 60 g/eq to 180 g/eq; and the adduct has a viscosity offrom 500 mPa·s to 50,000 mPa·s at 25° C. and a hydrogen equivalentweight of from 60 g/eq to 100 g/eq.
 6. The curable composition of claim1, wherein the curable composition has a viscosity of from 1,000 mPa·sto 10,000 mPa·s at 25° C.; and a pot life of from 15 minutes to 90minutes.
 7. An article comprising a substrate and a coating on thesubstrate, wherein the coating includes a cured composition of thecurable composition of claim
 1. 8. The article of claim 7, wherein theadduct is formed from the combination of the epoxy compound and a firstamine selected from the group consisting of isophorone diamine,m-xylylenediamine, and combinations thereof; and the Mannich base isformed from a reaction of formaldehyde, para-tertiary-butylphenol, andisophorone diamine.
 9. The article of claim 7, wherein the adductcomprises from 1 weight percent to 90 weight percent of the hardenercomponent; and the Mannich base comprises from 10 weight percent to 90weight percent of the hardener component, such that the weight percentof the adduct and the weight percent of the Mannich base equal onehundred weight percent of the hardener component.
 10. The article ofclaim 7, wherein the cured composition has a glass transitiontemperature within a range of from 40° C. to 80° C.; and a hardnesswithin a range of from 76 to 84 on a Shore D hardness scale.